U.S. patent number 10,207,949 [Application Number 15/821,710] was granted by the patent office on 2019-02-19 for glass fiber, composition for producing the same, and composite material comprising the same.
This patent grant is currently assigned to JUSHI GROUP CO., LTD.. The grantee listed for this patent is JUSHI GROUP CO., LTD.. Invention is credited to Guorong Cao, Guijiang Gu, Wenzhong Xing, Lin Zhang.
United States Patent |
10,207,949 |
Zhang , et al. |
February 19, 2019 |
Glass fiber, composition for producing the same, and composite
material comprising the same
Abstract
A composition for producing a glass fiber, including the
following components with corresponding percentage amounts by
weight: SiO.sub.2: 57.1-61.4%; Al.sub.2O.sub.3: 17.1-21%; MgO:
10.1-14.5%; Y.sub.2O.sub.3: 1.1-4.3%; CaO: <6.5%;
Li.sub.2O+Na.sub.2O+K.sub.2O: .ltoreq.1%; Li.sub.2O: .ltoreq.0.75%;
TiO.sub.2: <1.8%; and Fe.sub.2O.sub.3: 0.05-1.2%. The total
weight percentage of the above components in the composition is
greater than or equal to 98%. The weight percentage ratio of
Al.sub.2O.sub.3 to SiO.sub.2 is greater than or equal to 0.285. The
invention also provides a glass fiber produced using the
composition and a composite material including the glass fiber.
Inventors: |
Zhang; Lin (Tongxiang,
CN), Xing; Wenzhong (Tongxiang, CN), Cao;
Guorong (Tongxiang, CN), Gu; Guijiang (Tongxiang,
CN) |
Applicant: |
Name |
City |
State |
Country |
Type |
JUSHI GROUP CO., LTD. |
Tongxiang |
N/A |
CN |
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Assignee: |
JUSHI GROUP CO., LTD.
(Tongxiang, CN)
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Family
ID: |
60326217 |
Appl.
No.: |
15/821,710 |
Filed: |
November 22, 2017 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20180208497 A1 |
Jul 26, 2018 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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PCT/CN2017/073447 |
Feb 14, 2017 |
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Foreign Application Priority Data
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Jan 26, 2017 [CN] |
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2017 1 0057315 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C03C
3/087 (20130101); C03C 13/00 (20130101); C03C
3/095 (20130101); C03C 2213/00 (20130101) |
Current International
Class: |
C03C
13/00 (20060101); C03C 3/087 (20060101); C03C
3/095 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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105693100 |
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Jun 2016 |
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CN |
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105731814 |
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Jul 2016 |
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CN |
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105753329 |
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Jul 2016 |
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CN |
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106007369 |
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Oct 2016 |
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CN |
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106082639 |
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Nov 2016 |
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CN |
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2129102 |
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Apr 1999 |
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RU |
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2607331 |
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Jan 2017 |
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RU |
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201615585 |
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May 2016 |
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TW |
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2016165506 |
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Oct 2016 |
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WO |
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2016165530 |
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Oct 2016 |
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WO |
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WO-2017197933 |
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Nov 2017 |
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WO |
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Other References
The World Intellectual Property Organization (WIPO) International
Search Report for PCT/CN2017/073447 dated Oct. 31, 2017 4 Pages.
cited by applicant .
Written opinion dated Jan. 2, 2018 for PCT/CN2017/073447. cited by
applicant.
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Primary Examiner: Bolden; Elizabeth A.
Attorney, Agent or Firm: Anova Law Group, PLLC
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of International Patent
Application No. PCT/CN2017/073447 with an international filing date
of Feb. 14, 2017, designating the United States, now pending, and
further claims foreign priority to Chinese Patent Application No.
201710057315.3 filed Jan. 26, 2017. The contents of all of the
aforementioned applications, including any intervening amendments
thereto, are incorporated herein by reference.
Claims
The invention claimed is:
1. A composition for producing a glass fiber, comprising the
following components with corresponding percentage amounts by
weight: TABLE-US-00028 SiO.sub.2 57.1-61.4%; Al.sub.2O.sub.3
17.1-21%; MgO 10.1-14.5%; Y.sub.2O.sub.3 1.1-4.3%; CaO <6.5%;
Li.sub.2O + Na.sub.2O + K.sub.2O .ltoreq.1%; Li.sub.2O
.ltoreq.0.75%; TiO.sub.2 <1.8%; and Fe.sub.2O.sub.3
0.05-1.2%;
wherein a total weight percentage of the above components is
greater than or equal to 98%; and a weight percentage ratio
Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305, and a
weight percentage ratio
(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or
equal to 7.45.
2. The composition of claim 1, comprising 10.3-14 wt. % of MgO.
3. The composition of claim 1, wherein a weight percentage of MgO
is greater than 11% and less than or equal to 13.5%.
4. The composition of claim 1, comprising 0.05-0.7 wt. % of
Li.sub.2O.
5. The composition of claim 1, wherein a total weight percentage of
Y.sub.2O.sub.3 2.3-3.9%.
6. The composition of claim 1, wherein a total weight percentage of
Li.sub.2O+Na.sub.2O+K.sub.2O is 0.25%-0.98%.
7. The composition of claim 1, wherein a total weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
8. The composition of claim 1, further comprising no more than 2
wt. % of CeO.sub.2, SrO, La.sub.2O.sub.3, ZnO, B.sub.2O.sub.3,
ZrO.sub.2, or a mixture thereof.
9. The composition of claim 1, wherein a weight percentage ratio
Al.sub.2O.sub.3/SiO.sub.2 is 0.305-0.357.
10. The composition of claim 1, wherein a weight percentage ratio
MgO/CaO is greater than or equal to 1.6.
11. The composition of claim 1, wherein a weight percentage ratio
(Y.sub.2O.sub.3+MgO)/SiO.sub.2 is greater than or equal to 0.2.
12. The composition of claim 1, comprising the following components
with corresponding percentage amounts by weight: TABLE-US-00029
SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO 10.1-14.5%;
Y.sub.2O.sub.3 2-4.2%; CaO .ltoreq.6.3%; Li.sub.2O + Na.sub.2O +
K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2 <1.4%;
and Fe.sub.2O.sub.3 0.05-1%;
wherein a total weight percentage of the above components is
greater than or equal to 98%; and a weight percentage ratio
Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305.
13. The composition of claim 1, comprising the following components
with corresponding percentage amounts by weight: TABLE-US-00030
SiO.sub.2 58-60.4% Al.sub.2O.sub.3 17.5-20.5% MgO 10.3-14%
Y.sub.2O.sub.3 2-4% CaO 2-6% Li.sub.2O + Na.sub.2O + K.sub.2O
.ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2 <1.4%
Fe.sub.2O.sub.3 0.05-1%;
wherein a total weight percentage of the above components is
greater than or equal to 98%; and a weight percentage ratio
Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305.
14. The composition of claim 1, comprising the following components
with corresponding percentage amounts by weight: TABLE-US-00031
SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO 10.3-14%;
Y.sub.2O.sub.3 2-4%; CaO .ltoreq.6.3%; Li.sub.2O + Na.sub.2O +
K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2 <1.4%;
and Fe.sub.2O.sub.3 0.05-1%;
wherein a total weight percentage of the above components is
greater than or equal to 98%; a weight percentage ratio
Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305; and a
weight percentage ratio
(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or
equal to 7.45.
15. The composition of claim 1, comprising the following components
with corresponding percentage amounts by weight: TABLE-US-00032
SiO.sub.2 58-60.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO 10.5-14%;
Y.sub.2O.sub.3 2-4%; CaO 2-6%; Li.sub.2O + Na.sub.2O + K.sub.2O
.ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2 <1.4%; and
Fe.sub.2O.sub.3 0.05-1%;
wherein a total weight percentage of the above components is
greater than or equal to 98%; a weight percentage ratio
Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305; a
weight percentage ratio
(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or
equal to 7.45; and a total weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
16. The composition of claim 1, comprising the following components
with corresponding percentage amounts by weight: TABLE-US-00033
SiO.sub.2 58-60.4%; Al.sub.2O.sub.3 17.7-20.1%; MgO greater than
11% but not greater than 13.5%; Y.sub.2O.sub.3 2-4%; CaO 2.3-5.8%;
Li.sub.2O + Na.sub.2O + K.sub.2O .ltoreq.1%; Li.sub.2O 0.05-0.7%;
TiO.sub.2 <1.4%; and Fe.sub.2O.sub.3 0.05-1%;
wherein a total weight percentage of the above components is
greater than or equal to 98%; a weight percentage ratio
Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal 0.305; a weight
percentage ratio (Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is
greater than or equal to 7.45; and a total weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
29.1%.
17. The composition of claim 1, comprising the following components
with corresponding percentage amounts by weight: TABLE-US-00034
SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO 10.1-14.5%;
Y.sub.2O.sub.3 2-4.2%; CaO .ltoreq.6.3%; Li.sub.2O + Na.sub.2O +
K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2 <1.4%;
Fe.sub.2O.sub.3 0.05-1%; SrO + CeO.sub.2 + F.sub.2 <2%; SrO
0-1.7%; CeO.sub.2 0-0.55%; and F.sub.2 0-0.5%;
wherein a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is
greater than or equal to 0.305; and a weight percentage ratio
(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or
equal to 7.45.
18. A glass fiber, being produced using the composition of claim
1.
19. A composite material, comprising the glass fiber of claim 18.
Description
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a glass fiber, a composition for
producing the same, and a composite material comprising the
same.
Description of the Related Art
In general, the production of conventional glass fibers faces such
difficulties as excessively high liquidus temperature of glass,
excessively high rate of crystallization, high forming temperature,
refining difficulty of molten glass and a narrow temperature range
(.DELTA.T) for fiber formation. In addition,
conventionally-produced glass fibers have relatively low strength
and modulus.
SUMMARY OF THE INVENTION
It is one objective of the present disclosure to provide a
composition for producing a glass fiber. The resulting glass fiber
has relatively high strength and modulus, and relatively low
crystallization rate and liquidus temperature; meanwhile, the
composition for producing a glass fiber lowers the high temperature
viscosity, forming temperature and bubbling ratio of the glass, all
of which helps to reduce the energy consumption during
production.
The composition for producing a glass fiber of the present
invention is particularly suitable for large-scale production with
refractory-lined furnaces.
To achieve the above objective, in accordance with one embodiment
of the present disclosure, there is provided a composition for
producing glass fiber, the composition comprising percentage
amounts by weight, as follows:
TABLE-US-00001 SiO.sub.2 57.1-61.4%; Al.sub.2O.sub.3 17.1-21%; MgO
10.1-14.5%; Y.sub.2O.sub.3 1.1-4.3%; CaO <6.5%; Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2
<1.8%; and Fe.sub.2O.sub.3 0.05-1.2%.
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, and the weight
percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or
equal to 0.285.
In a class of this embodiment, the composition comprises the
following components expressed as percentage amounts by weight:
TABLE-US-00002 SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%;
MgO 10.1-14.5%; Y.sub.2O.sub.3 2-4.2%; CaO .ltoreq.6.3%; Li.sub.2O
+ Na.sub.2O + K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%;
TiO.sub.2 <1.4%; and Fe.sub.2O.sub.3 0.05-1%.
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, and the weight
percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or
equal to 0.285.
In a class of this embodiment, the composition comprises the
following components expressed as percentage amounts by weight:
TABLE-US-00003 SiO.sub.2 58-60.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO
10.3-14%; Y.sub.2O.sub.3 2-4%; CaO 2-6%; Li.sub.2O + Na.sub.2O +
K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2 <1.4%;
and Fe.sub.2O.sub.3 0.05-1%.
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, and the weight
percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or
equal to 0.285.
In a class of this embodiment, the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5.
In a class of this embodiment, the weight percentage ratio
C1=Al.sub.2O.sub.3/SiO.sub.2 is 0.289-0.357.
In a class of this embodiment, the weight percentage ratio
C3=(Y.sub.2O.sub.3+MgO)/SiO.sub.2 is greater than or equal to
0.2.
In a class of this embodiment, the content range of MgO is 10.3-14%
in percentage amounts by weight.
In a class of this embodiment, the content range of MgO is greater
than 11% but not greater than 13.5% in percentage amounts by
weight.
In a class of this embodiment, the content range of MgO is
11.2-13.5% in percentage amounts by weight.
In a class of this embodiment, the composition contains one or more
components selected from the group consisting of CeO.sub.2, SrO,
La.sub.2O.sub.3, ZnO, B.sub.2O.sub.3 and ZrO.sub.2, with the
combined weight percentages less than 2%.
In a class of this embodiment, the composition contains SrO in a
content of 0-1.7% in percentage amounts by weight.
In a class of this embodiment, the composition contains CeO.sub.2
in a content of 0-0.55% in percentage amounts by weight.
In a class of this embodiment, the total weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
In a class of this embodiment, the total weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
29.1%;
In a class of this embodiment, the weight percentage ratio of
MgO/CaO is greater than or equal to 1.6.
In a class of this embodiment, the content range of Li.sub.2O is
0.05-0.7% in percentage amounts by weight.
In a class of this embodiment, the total weight percentage of
Li.sub.2O+Na.sub.2O+K.sub.2O is 0.25-0.98%.
In a class of this embodiment, the composition comprises the
following components expressed as percentage amounts by weight:
TABLE-US-00004 SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%;
MgO 10.3-14%; Y.sub.2O.sub.3 2-4%; CaO .ltoreq.6.3%; Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2
<1.4%; and Fe.sub.2O.sub.3 0.05-1%.
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the weight percentage
ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to
0.285; and the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5.
In a class of this embodiment, the composition comprises the
following components expressed as percentage amounts by weight:
TABLE-US-00005 SiO.sub.2 58-60.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO
10.5-14%; Y.sub.2O.sub.3 2-4%; CaO 2-6%; Li.sub.2O + Na.sub.2O +
K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2 <1.4%;
and Fe.sub.2O.sub.3 0.05-1%;
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the weight percentage
ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to
0.285; the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
In a class of this embodiment, the composition comprises the
following components expressed as percentage amounts by weight:
TABLE-US-00006 SiO.sub.2 58-60.4%; Al.sub.2O.sub.3 17.7-20.1%; MgO
greater than 11% but not greater than 13.5%; Y.sub.2O.sub.3 2-4%;
CaO 2.3-5.8%; Li.sub.2O + Na.sub.2O + K.sub.2O .ltoreq.1%;
Li.sub.2O 0.05-0.7%; TiO.sub.2 <1.4%; and Fe.sub.2O.sub.3
0.05-1%;
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the weight percentage
ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to
0.285; the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
29.1%.
In a class of this embodiment, the content of Y.sub.2O.sub.3 is
2.3-3.9% in percentage amounts by weight.
In a class of this embodiment, the composition contains
La.sub.2O.sub.3 in a content of 0-0.05% in percentage amounts by
weight.
In a class of this embodiment, the composition comprises the
following components expressed as percentage amounts by weight:
TABLE-US-00007 SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%;
MgO 10.1-14.5%; Y.sub.2O.sub.3 2-4.2%; CaO .ltoreq.6.3%; Li.sub.2O
+ Na.sub.2O + K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%;
TiO.sub.2 <1.4%; Fe.sub.2O.sub.3 0.05-1%; SrO + CeO.sub.2 +
F.sub.2 <2%; SrO 0-1.7%; CeO.sub.2 0-0.55%; and F.sub.2
0-0.5%;
In addition, the weight percentage ratio
C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.285, and
the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5.
According to another aspect of this invention, a glass fiber
produced with the composition for producing a glass fiber is
provided.
According to yet another aspect of this invention, a composite
material incorporating the glass fiber is provided.
The main inventive points of the composition for producing a glass
fiber according to this invention lie in that, by introducing high
contents of Y.sub.2O.sub.3 and MgO, significantly reducing the
content of CaO, controlling the content of alkali metal oxides and
keeping tight control on the ratios of Al.sub.2O.sub.3/SiO.sub.2,
(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 and
(Y.sub.2O.sub.3+MgO)/SiO.sub.2 respectively, while reasonably
configuring the content ranges of Al.sub.2O.sub.3, SiO.sub.2,
Y.sub.2O.sub.3, MgO, Li.sub.2O, CaO and
Al.sub.2O.sub.3+MgO+Li.sub.2O, utilizing the special compensation
effect and accumulation effect of yttrium in the glass structure as
well as the synergistic effect among the ions of yttrium, magnesium
and lithium, and effectively controlling the Al/Si ratio and the
rare earths content, the composition enables an appropriate amount
of vacancies that leads to more orderly ion packing, more compact
stacking structure of the glass and higher difficulty of ions
reorganization and arrangement during the crystallization process.
Therefore, the composition for producing a glass fiber of this
invention significantly increases the glass strength and modulus,
effectively reduces the glass crystallization rate, secures a
desirable temperature range (.DELTA.T) for fiber formation and
enhances the refinement of molten glass, thus making it
particularly suitable for high performance glass fiber production
with refractory-lined furnaces.
Specifically, the composition for producing a glass fiber according
to the present invention comprises the following components
expressed as percentage amounts by weight:
TABLE-US-00008 SiO.sub.2 57.1-61.4%; Al.sub.2O.sub.3 17.1-21%; MgO
10.1-14.5%; Y.sub.2O.sub.3 1.1-4.3%; CaO <6.5%; Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1%; Li.sub.2O .ltoreq.0.75%; TiO.sub.2
<1.8%; and Fe.sub.2O.sub.3 0.05-1.2%;
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, and the weight
percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or
equal to 0.285.
The effect and content of each component in the composition for
producing a glass fiber is described as follows:
SiO.sub.2 is a main oxide forming the glass network and has the
effect of stabilizing all the components. Too low of a SiO.sub.2
content will affect the mechanical properties of the glass; too
high of a content will cause the glass viscosity and liquidus
temperature to be excessively high thereby resulting in difficulty
for large-scale production. Therefore, in the composition for
producing a glass fiber of the present invention, the content range
of SiO.sub.2 is 57.1-61.4%. Preferably, the SiO.sub.2 content range
can be 57.4-61.4%, more preferably 58-60.4%, and still more
preferably greater than or equal to 58% but lower than 60%.
Al.sub.2O.sub.3 is another main oxide forming the glass network.
When combined with SiO.sub.2, it can have a substantive effect on
the mechanical properties of the glass and a significant effect on
preventing glass phase separation and on crystallization
resistance. Too low of an Al.sub.2O.sub.3 content will make it
impossible to obtain sufficiently high mechanical properties,
especially modulus; too high of a content will significantly
increase the risks of glass phase separation and crystallization.
The content range of Al.sub.2O.sub.3 in this invention is 17.1-21%.
Preferably, the Al.sub.2O.sub.3 content can be 17.5-20.5%, more
preferably 17.7-20.1%. In addition, the sum of the weight
percentages of SiO.sub.2+Al.sub.2O.sub.3 can be 75.5-82%, which
will not only ensure sufficiently high mechanical properties but
also enable the large-scale production with refractory-lined
furnaces at relatively low temperatures. Preferably, the sum of the
weight percentages of SiO.sub.2+Al.sub.2O.sub.3 can be 76-81%.
Meanwhile, the weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2
is greater than or equal to 0.285, so that the glass can have
higher mechanical properties and crystallization resistance as well
as broader temperature range (.DELTA.T) for fiber formation. The
present invention not only ensures an effective packing of aluminum
ions and provide sufficient vacancies for rare earth ions with
relatively big radiuses, and also minimizes the risk of formation
of glass structural stress and further enhances the stacking effect
of the glass structure. To achieve these desired features,
preferably the range of the weight percentage ratio
C1=Al.sub.2O.sub.3/SiO.sub.2 can be 0.285-0.357, more preferably
can be 0.289-0.357, even more preferably can be 0.291-0.353, and
still even more preferably can be 0.294-0.346.
Y.sub.2O.sub.3 is an important rare earth oxide. The inventors find
that a relatively high amount of Y.sub.2O.sub.3 contained in the
glass composition of this invention would noticeably increase the
glass strength and modulus and inhibit the glass crystallization.
As the external ions at the gaps of the glass network, Y.sup.3+
ions have large coordination numbers, high field strength and
electric charge, and high accumulation capability. For these
features, Y.sup.3+ ions can help not only to improve the structural
stability of the glass and increase the glass strength and modulus,
but also effectively prevent the movement and arrangement of other
ions to minimize the crystallization tendency of the glass. The
inventors find from experiments that the above technical effects
are not noticeable when a small amount of Y.sub.2O.sub.3 is
introduced. Meanwhile, as Y.sup.3+ ions have relatively big
radiuses (0.09 nm) compared with those of Al.sup.3+ (0.0535 nm),
Mg.sup.2+ (0.072 nm) and Li.sup.+ (0.076 nm) ions, the introduced
amount of Y.sub.2O.sub.3 exceeding a certain value would lead to
insufficient vacanies for the big Y.sup.3+ ions to fill, thus
affecting the compact stacking of the glass structure and
significantly increasing the glass density and structural stress.
Therefore, in the composition for producing a glass fiber of this
invention, the content range of Y.sub.2O.sub.3 is 1.1-4.3%,
preferably 2-4.2%, more preferably 2-4%, and still more preferably
2.3-3.9%.
Additionally, in order to achieve a better structural stacking,
further increase the glass strength and modulus and acquire a
favorable glass density, the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 in this invention
can be greater than or equal to 6.5, so that the proportions of the
various ions with different radiuses can be effectively controlled
for desired mechanical properties and compact stacking structure of
the glass. Preferably, the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 can be greater
than or equal to 7.0, and more preferably can be 7.2-15.
Furthermore, the range of the weight percentage ratio of
Al.sub.2O.sub.3+MgO+Li.sub.2O can be greater than or equal to
28.1%, preferably greater than or equal to 28.6%, more preferably
greater than or equal to 29.1%, and still more preferably greater
than or equal to 29.6%.
In this invention, MgO and CaO mainly control the glass
crystallization and regulate the glass viscosity and the rate of
hardening of molten glass, and a high content of MgO has a
favorable effect on the mechanical properties of the glass. With
respect to the control of the glass crystallization and improvement
of mechanical properties, the inventors have obtained unexpected
effects by raising the MgO content and controlling the ratios of
MgO/CaO and (Y.sub.2O.sub.3+MgO)/SiO.sub.2. Relevant data shows
that, for the conventional high-performance glass based on the
MgO--CaO--Al.sub.2O.sub.3--SiO.sub.2 system, where the content of
CaO is relatively high, typically greater than 10% or even 12%, the
crystal phases it contains after glass crystallization include
mainly diopside (CaMgSi.sub.2O.sub.6) and anorthite
(CaAl.sub.2Si.sub.2O.sub.8). The competitive growth between these
two crystals during the crystallization process is not so vigorous
that no effective control of the crystallization rate can be
achieved. Therefore, in this invention, the content of CaO is
greatly reduced while the content of MgO is increased to create a
shortage of CaO for crystallization, and consequently the crystal
phases obtained after glass crystallization include mainly
cordierite (Mg.sub.2Al.sub.4Si.sub.5O.sub.8) or a mixture of
cordierite, enstatite (MgSiO.sub.3) and anorthite, thereby
effectively inhibiting the crystallization rate of the glass. At
the same time, considering the differences of ionic radiuses and
field strengths between Y.sup.3+ ions and Mg.sup.2+ ions, the
ratios of each of these two ions to silica are rationally
controlled, so that not only can a better effect of structural
stacking be achieved, but also the movement and arrangement of
Mg.sup.2+ ions can be further impeded and hence the effect of
inhibiting the crystalization rate is strengthened.
Therefore, in the composition for producing a glass fiber of the
present invention, the content range of MgO can be 10.1-14.5%,
preferably 10.3-14%, more preferably 10.5-14%, even more preferably
greater than 11% but not greater than 13.5%, and still even more
preferably 11.2-13.5%; the content range of CaO can be lower than
6.5%, preferably not greater than 6.3%, more preferably can be
2-6%, and still more preferably 2.3-5.8%; the range of the weight
percentage ratio C3=(Y.sub.2O.sub.3+MgO)/SiO.sub.2 can be greater
than or equal to 0.2, preferably greater than or equal to 0.21, and
more preferably greater than or equal to 0.23; and the range of the
weight percentage ratio MgO/CaO can be greater than or equal to
1.6, preferably greater than or equal to 1.75, and more preferably
greater than or equal to 1.9.
Both K.sub.2O and Na.sub.2O can reduce glass viscosity and are good
fluxing agents. Compared with Na.sub.2O and K.sub.2O, Li.sub.2O can
significantly reduce glass viscosity thereby improving the glass
melting performance. In addition, a small amount of Li.sub.2O
provides considerable free oxygen, which helps more aluminum ions
to form tetrahedral coordination, enhances the network structure of
the glass and further improves the mechanical properties of glass.
However, as too many alkali metal ions in the glass composition
would affect the stability and corrosion resistance of the glass,
the introduced amount should be limited. Therefore, in the
composition for producing a glass fiber of the present invention,
the content range of Li.sub.2O+Na.sub.2O+K.sub.2O is not greater
than 1%, and the content range of Li.sub.2O is not greater than
0.75%. Preferably, the content range of Li.sub.2O is not greater
than 0.7%, more preferably can be 0.05-0.7%, and still more
preferably can be 0.1-0.65%. Preferably, the content range of
Li.sub.2O+Na.sub.2O+K.sub.2O can be not greater than 0.98%, more
preferably can be 0.25-0.98%, and still more preferably can be
0.3-0.95%. In addition, as both K.sup.+ and Na.sup.+ ions have
relatively large radiuses (0.138 nm and 0.102 nm, respectively),
when Y.sub.2O.sub.3 is introduced at a high amount, the sum of
Na.sub.2O+K.sub.2O should be limited so as not to affect the
stacking effect of the glass structure. Therefore, the range of the
weight percentage ratio Na.sub.2O+K.sub.2O can be lower than 0.7%,
preferably lower than 0.55%.
TiO.sub.2 can not only reduce the glass viscosity at high
temperature, but also has a certain fluxing effect. However, since
titanium ions in combination with ferric ions can have a certain
coloring effect, which will affect the appearance of glass
fiber-reinforced articles, the introduced amount should be limited.
Therefore, in the composition for producing a glass fiber of the
present invention, the content range of TiO.sub.2 is lower than
1.8%, preferably lower than 1.4%, and more preferably not greater
than 0.8%.
Fe.sub.2O.sub.3 facilitates the melting of glass and can also
improve the crystallization performance of glass. However, since
ferric ions and ferrous ions have a coloring effect, the introduced
amount should be limited. Therefore, in the composition for
producing a glass fiber of the present invention, the content range
of Fe.sub.2O.sub.3 is 0.05-1.2%, preferably 0.05-1%.
In addition, the composition for producing a glass fiber of the
present invention can include small amounts of other components
with a total content not greater than 2%. Furthermore, the
composition for producing a glass fiber of the present invention
can include one or more components with a total content not greater
than 2% selected from the group consisting of CeO.sub.2, SrO,
La.sub.2O.sub.3, ZnO, B.sub.2O.sub.3 and ZrO.sub.2. Furthermore,
the composition for producing a glass fiber of the present
invention can include one or more components with a total content
not greater than 1% selected from the group consisting of
La.sub.2O.sub.3, ZnO, B.sub.2O.sub.3 and ZrO.sub.2. Furthermore,
the composition for producing a glass fiber of the present
invention can include SrO with a content range of 0-1.7%.
Furthermore, the composition for producing a glass fiber of the
present invention can include SrO with a content range of 0.1-1.3%.
Furthermore, the composition for producing a glass fiber of the
present invention can include either or both of the components
CeO.sub.2 and SrO with a total content not greater than 1.3%.
Furthermore, the composition for producing a glass fiber of the
present invention can include CeO.sub.2 with a content range of
0-0.55%. Furthermore, the composition for producing a glass fiber
of the present invention can include CeO.sub.2 with a content range
of 0-0.25%. Furthermore, the composition for producing a glass
fiber of the present invention can include F.sub.2 with a content
range of 0-0.5% and generally in the form of impurities contained
in the glass raw materials. Furthermore, the composition for
producing a glass fiber of the present invention may not include
B.sub.2O.sub.3 that is generally introduced in the form of
impurities contained in the glass raw materials. Furthermore, the
composition for producing a glass fiber of the present invention
can include La.sub.2O.sub.3 with a content range of 0-0.05%
Furthermore, the composition for producing a glass fiber of the
present invention includes SiO.sub.2, Al.sub.2O.sub.3, MgO,
Y.sub.2O.sub.3, CaO, Li.sub.2O, Na.sub.2O, K.sub.2O, TiO.sub.2,
Fe.sub.2O.sub.3 and other components with a total content equaling
to or greater than 99%. Furthermore, the composition for producing
a glass fiber of the present invention includes SiO.sub.2,
Al.sub.2O.sub.3, MgO, Y.sub.2O.sub.3, CaO, Li.sub.2O, Na.sub.2O,
K.sub.2O, TiO.sub.2, Fe.sub.2O.sub.3 and other components with a
total content equaling to or greater than 99.5%.
In the composition for producing a glass fiber of the present
invention, the beneficial effects produced by the aforementioned
selected ranges of the components will be explained by way of
examples through the specific experimental data.
The following are examples of preferred content ranges of the
components contained in the composition for producing a glass fiber
according to the present invention.
Composition 1
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00009 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.1-14.5% Y.sub.2O.sub.3 2-4.2% CaO .ltoreq.6.3% Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2
<1.4% Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, and the weight
percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or
equal to 0.285.
Composition 2
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00010 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.1-14.5% Y.sub.2O.sub.3 2-4.2% CaO .ltoreq.6.3% Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2
<1.4% Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, SrO in an amount of
0-1.7% by weight is also present in the above composition, and the
range of the weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2
is 0.285-0.357.
Composition 3
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00011 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.1-14.5% Y.sub.2O.sub.3 2-4.2% CaO .ltoreq.6.3% Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2
<1.4% Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, SrO in an amount of
0-1.7% by weight and CeO.sub.2 in an amount of 0-0.55% by weight
are also present in the above composition, and the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is
0.285-0.357.
Composition 4
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00012 SiO.sub.2 58-60.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.3-14% Y.sub.2O.sub.3 2-4% CaO 2-6% Li.sub.2O + Na.sub.2O +
K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2 <1.4%
Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, and the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater
than or equal to 0.285.
Composition 5
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00013 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.1-14.5% Y.sub.2O.sub.3 2-4.2% CaO .ltoreq.6.3% Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2
<1.4% Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%, CeO.sub.2 in an
amount of 0-0.55% by weight is also present in the above
composition, and the range of the weight percentage ratio
C1=Al.sub.2O.sub.3/SiO.sub.2 is 0.289-0.357.
Composition 6
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00014 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.1-14.5% Y.sub.2O.sub.3 2-4.2% CaO .ltoreq.6.3% Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2
<1.4% Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater
than or equal to 0.285; the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
Composition 7
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00015 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.3-14% Y.sub.2O.sub.3 2-4% CaO .ltoreq.6.3% Li.sub.2O + Na.sub.2O
+ K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2 <1.4%
Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater
than or equal to 0.285; and the range of the weight percentage
ratio C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater
than or equal to 6.5.
Composition 8
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00016 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.5-14% Y.sub.2O.sub.3 2-4% CaO .ltoreq.6.3% Li.sub.2O + Na.sub.2O
+ K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2 <1.4%
Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is
0.285-0.357; and the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 7.0.
Composition 9
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00017 SiO.sub.2 58-60.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.5-14% Y.sub.2O.sub.3 2-4% CaO 2-6% Li.sub.2O + Na.sub.2O +
K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2 <1.4%
Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater
than or equal to 0.285; the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
Composition 10
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00018 SiO.sub.2 58-60.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.3-14% Y.sub.2O.sub.3 2-4% CaO 2-6% Li.sub.2O + Na.sub.2O +
K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2 <1.4%
Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is
0.291-0.353; the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 7.0; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
Composition 11
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00019 SiO.sub.2 58-60.4% Al.sub.2O.sub.3 17.5-20.5% MgO
greater than 11% but not greater than 13.5% Y.sub.2O.sub.3 2-4% CaO
2-6% Li.sub.2O + Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O
.ltoreq.0.75% TiO.sub.2 <1.4% Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater
than or equal to 0.285; the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
Composition 12
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00020 SiO.sub.2 58-60.4% Al.sub.2O.sub.3 17.7-20.1% MgO
greater than 11% but not greater than 13.5% Y.sub.2O.sub.3 2.3-3.9%
CaO 2.3-5.8% Li.sub.2O + Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O
0.05-0.7% TiO.sub.2 <1.4% Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater
than or equal to 0.285; the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
29.1%.
Composition 13
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00021 SiO.sub.2 not lower than 58% but lower than 60%
Al.sub.2O.sub.3 17.7-20.1% MgO greater than 11% but not greater
than 13.5% Y.sub.2O.sub.3 2.3-3.9% CaO 2.3-5.8% Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O 0.05-0.7% TiO.sub.2
<1.4% Fe.sub.2O.sub.3 0.05-1%
In addition, the combined weight percentage of the components
listed above is greater than or equal to 98%; the range of the
weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater
than or equal to 0.285; the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 7.0; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
29.1%.
Composition 14
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00022 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.1-14.5% Y.sub.2O.sub.3 2-4.2% CaO .ltoreq.6.3% Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2
<1.4% Fe.sub.2O.sub.3 0.05-1% SrO + CeO.sub.2 + F.sub.2 <2%
SrO 0-1.7% CeO.sub.2 0-0.55% F.sub.2 0-0.5%
In addition, the range of the weight percentage ratio
C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.285, and
the range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 6.5.
Composition 15
The high-performance composition for producing a glass fiber
according to the present invention comprises the following
components expressed as percentage amounts by weight:
TABLE-US-00023 SiO.sub.2 57.4-61.4% Al.sub.2O.sub.3 17.5-20.5% MgO
10.3-14% Y.sub.2O.sub.3 2-4.2% CaO .ltoreq.6.3% Li.sub.2O +
Na.sub.2O + K.sub.2O .ltoreq.1% Li.sub.2O .ltoreq.0.75% TiO.sub.2
<1.4% Fe.sub.2O.sub.3 0.05-1% SrO + CeO.sub.2 + F.sub.2 <2%
SrO 0-1.7% CeO.sub.2 0-0.55% F.sub.2 0-0.5%
In addition, the range of the weight percentage ratio
C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.285; the
range of the weight percentage ratio
C2=(Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than
or equal to 7.0; and the combined weight percentage of
Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to
28.1%.
DETAILED DESCRIPTION OF THE INVENTION
In order to better clarify the purposes, technical solutions and
advantages of the examples of the present invention, the technical
solutions in the examples of the present invention are clearly and
completely described below. Obviously, the examples described
herein are just part of the examples of the present invention and
are not all the examples. All other exemplary embodiments obtained
by one skilled in the art on the basis of the examples in the
present invention without performing creative work shall all fall
into the scope of protection of the present invention. What needs
to be made clear is that, as long as there is no conflict, the
examples and the features of examples in the present application
can be arbitrarily combined with each other.
The basic concept of the present invention is that the components
of the composition for producing a glass fiber expressed as
percentage amounts by weight are: 57.1-61.4% SiO.sub.2, 17.1-21%
Al.sub.2O.sub.3, 10.1-14.5% MgO, 1.1-4.3% Y.sub.2O.sub.3, lower
than 6.5% CaO, not greater than 1% Li.sub.2O+Na.sub.2O+K.sub.2O,
not greater than 0.75% Li.sub.2O, lower than 1.8% TiO.sub.2 and
0.05-1.2% Fe.sub.2O.sub.3, wherein the range of the combined weight
percentage of these components is greater than or equal to 98% and
the range of the weight percentage ratio
C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.285. The
composition can significantly increase the glass strength and
modulus, effectively reduce the glass crystallization rate, secure
a desirable temperature range (.DELTA.T) for fiber formation and
enhance the refinement of molten glass, thus making it particularly
suitable for high performance glass fiber production with
refractory-lined furnaces.
The specific content values of SiO.sub.2, Al.sub.2O.sub.3,
Y.sub.2O.sub.3, CaO, MgO, Li.sub.2O, Na.sub.2O, K.sub.2O,
Fe.sub.2O.sub.3 and TiO.sub.2 in the composition for producing a
glass fiber of the present invention are selected to be used in the
examples, and comparisons with S glass, traditional R glass and
improved R glass are made in terms of the following seven property
parameters,
(1) Forming temperature, the temperature at which the glass melt
has a viscosity of 10.sup.3 poise.
(2) Liquidus temperature, the temperature at which the crystal
nucleuses begin to form when the glass melt cools off--i.e., the
upper limit temperature for glass crystallization.
(3) .DELTA.T value, which is the difference between the forming
temperature and the liquidus temperature and indicates the
temperature range at which fiber drawing can be performed.
(4) Elastic modulus, the modulus defining the ability of glass to
resist elastic deformation, which is to be measured on bulk glass
as per ASTM E1876.
(5) Tensile strength, the maximum tensile stress that the glass
fiber can withstand, which is to be measured on impregnated glass
roving as per ASTM D2343.
(6) Crystallization area ratio, to be determined in a procedure set
out as follows: Cut the bulk glass appropriately to fit in with a
porcelain boat trough and then place the cut glass bar sample into
the porcelain boat. Put the porcelain boat with the glass bar
sample into a gradient furnace for crystallization and keep the
sample for heat preservation for 6 hours. Take the boat with the
sample out of the gradient furnace and air-cool it to room
temperature. Finally, examine and measure the amounts and
dimensions of crystals on the surfaces of each sample within the
temperature range of 1060-1130.degree. C. from a microscopic view
by using an optical microscope, and then calculate the area ratio
of crystallization. A high area ratio would mean a high
crystallization tendency and high crystallization rate.
(7) Amount of bubbles, to be determined in a procedure set out as
follows: Use specific molds to compress the glass batch materials
in each example into samples of same dimension, which will then be
placed on the sample platform of a high temperature microscope.
Heat the samples according to standard procedures up to the pre-set
spatial temperature 1500.degree. C. and then directly cool them off
with the cooling hearth of the microscope to the ambient
temperature without heat preservation. Finally, each of the glass
samples is examined under a polarizing microscope to determine the
amount of bubbles in the samples. A bubble is identified according
to a specific amplification of the microscope.
The aforementioned seven parameters and the methods of measuring
them are well-known to one skilled in the art. Therefore, these
parameters can be effectively used to explain the properties of the
composition for producing a glass fiber of the present
invention.
The specific procedures for the experiments are as follows: Each
component can be acquired from the appropriate raw materials. Mix
the raw materials in the appropriate proportions so that each
component reaches the final expected weight percentage. The mixed
batch melts and the molten glass refines. Then the molten glass is
drawn out through the tips of the bushings, thereby forming the
glass fiber. The glass fiber is attenuated onto the rotary collet
of a winder to form cakes or packages. Of course, conventional
methods can be used to deep process these glass fibers to meet the
expected requirement.
Comparisons of the property parameters of the examples of the
composition for producing a glass fiber according to the present
invention with those of the S glass, traditional R glass and
improved R glass are further made below by way of tables, where the
component contents of the composition for producing a glass fiber
are expressed as weight percentage. What needs to be made clear is
that the total amount of the components in the examples is slightly
less than 100%, and it should be understood that the remaining
amount is trace impurities or a small amount of components which
cannot be analyzed.
TABLE-US-00024 TABLE 1A A1 A2 A3 A4 A5 A6 A7 Component SiO.sub.2
59.50 59.50 59.50 58.85 58.85 58.85 58.85 Al.sub.2O.sub.3 18.70
18.70 18.70 19.05 19.05 19.05 19.05 CaO 6.40 6.00 5.10 6.30 5.80
5.10 4.10 MgO 11.30 11.30 11.30 10.30 10.80 11.50 12.50
Y.sub.2O.sub.3 1.80 2.30 3.20 3.40 3.40 3.40 3.40 Na.sub.2O 0.08
0.11 0.11 0.13 0.13 0.13 0.13 K.sub.2O 0.17 0.19 0.19 0.30 0.30
0.30 0.30 Li.sub.2O 0.70 0.65 0.65 0.47 0.47 0.47 0.47
Fe.sub.2O.sub.3 0.39 0.45 0.45 0.47 0.47 0.47 0.47 TiO.sub.2 0.64
0.52 0.52 0.53 0.53 0.53 0.53 CeO.sub.2 0.12 0.08 0.08 -- -- -- --
Ratio C1 0.314 0.314 0.314 0.324 0.324 0.324 0.324 C2 17.06 13.33
9.58 8.77 8.92 9.12 9.42 C3 0.220 0.229 0.244 0.233 0.241 0.253
0.270 Parameter Forming 1304 1307 1309 1314 1311 1309 1306
temperature/.degree. C. Liquidus 1218 1212 1207 1216 1211 1210 1217
temperature/ .degree. C. .DELTA.T/.degree. C. 86 95 102 98 100 99
89 Elastic 94.1 94.6 95.8 95.0 95.4 96.3 96.5 modulus/GPa Tensile
strength/ 3310 3400 3530 3460 3490 3590 3630 MPa Crystallization 19
15 9 11 10 7 9 area ratio/% Amount of 8 9 10 10 11 9 10
bubbles/pcs
TABLE-US-00025 TABLE 1B A8 A9 A10 A11 A12 A13 A14 Component
SiO.sub.2 58.85 58.85 59.00 59.00 59.00 60.00 60.00 Al.sub.2O.sub.3
19.05 19.05 18.80 18.80 18.80 18.30 17.70 CaO 3.10 2.80 6.00 5.30
4.40 2.00 4.90 MgO 13.50 14.00 11.10 11.40 12.00 12.40 11.70
Y.sub.2O.sub.3 3.40 3.40 3.00 3.40 3.70 4.20 3.30 Na.sub.2O 0.13
0.14 0.14 0.14 0.14 0.10 0.15 K.sub.2O 0.30 0.31 0.30 0.30 0.30
0.28 0.20 Li.sub.2O 0.47 0.30 0.50 0.50 0.50 0.60 0.65
Fe.sub.2O.sub.3 0.47 0.42 0.44 0.44 0.44 0.44 0.44 TiO.sub.2 0.53
0.53 0.52 0.52 0.52 0.48 0.46 SrO -- -- -- -- -- 1.00 -- ZrO.sub.2
-- -- -- -- -- -- 0.30 Ratio C1 0.324 0.324 0.319 0.319 0.319 0.305
0.295 C2 9.72 9.86 10.13 9.03 8.46 7.45 9.11 C3 0.287 0.296 0.239
0.251 0.266 0.277 0.250 Parameter Forming 1304 1305 1309 1307 1303
1325 1310 temperature/ .degree. C. Liquidus 1219 1224 1211 1207
1206 1220 1213 temperature/ .degree. C. .DELTA.T/.degree. C. 85 81
98 100 97 105 97 Elastic 95.7 95.2 95.1 96.0 97.3 96.8 95.6
modulus/ GPa Tensile 3540 3500 3460 3540 3630 3670 3510 strength/
MPa Crystallization 14 17 11 8 8 14 9 area ratio/% Amount of 9 8 10
9 9 10 9 bubbles/pcs
TABLE-US-00026 TABLE 1C A15 A16 A17 A18 A19 A20 A21 Component
SiO.sub.2 58.00 57.10 59.10 58.40 58.90 60.40 61.40 Al.sub.2O.sub.3
18.60 20.10 17.50 18.80 18.60 17.80 18.00 CaO 6.00 5.80 5.80 6.00
4.80 4.90 3.80 MgO 10.50 10.00 11.00 11.10 11.20 11.30 11.60
Y.sub.2O.sub.3 4.30 4.00 3.70 3.50 3.20 3.30 2.90 Na.sub.2O 0.12
0.10 0.15 0.30 0.21 0.10 0.15 K.sub.2O 0.22 0.20 0.30 0.35 0.31
0.20 0.30 Li.sub.2O 0.60 0.64 0.50 0 0.38 0.65 0.55 Fe.sub.2O.sub.3
0.46 0.46 0.45 0.45 0.44 0.46 0.44 TiO.sub.2 0.60 0.55 0.80 1.20
0.46 0.69 0.51 SrO 0.40 0.85 0.50 0.60 1.30 -- -- La.sub.2O.sub.3
-- -- -- -- -- -- 0.25 Ratio C1 0.321 0.352 0.296 0.322 0.316 0.295
0.293 C2 6.91 7.69 7.84 8.54 9.43 9.02 10.40 C3 0.255 0.245 0.249
0.250 0.244 0.242 0.236 Parameter Forming 1299 1301 1300 1305 1310
1317 1325 temperature/ .degree. C. Liquidus 1210 1200 1209 1212
1210 1227 1235 temperature/ .degree. C. .DELTA.T/.degree. C. 90 101
91 93 100 90 90 Elastic 96.3 96.0 95.5 96.1 96.5 95.1 94.9 modulus/
GPa Tensile 3560 3460 3480 3500 3540 3460 3430 strength/ MPa
Crystallization 7 13 8 9 11 16 19 area ratio/% Amount of 6 7 8 7 8
10 12 bubbles/pcs
TABLE-US-00027 TABLE 1D S Traditional Improved A22 A23 A24 A25
glass R glass R glass Component SiO.sub.2 57.40 60.00 59.50 58.80
65 60 60.75 Al.sub.2O.sub.3 20.50 19.00 18.40 18.70 25 25 15.80 CaO
4.10 3.90 4.90 5.30 -- 9 13.90 MgO 11.50 11.80 11.20 12.10 10 6
7.90 Y.sub.2O.sub.3 3.90 3.10 3.40 3.20 -- -- -- Na.sub.2O 0.08
0.12 0.12 0.15 trace trace 0.73 amount amount K.sub.2O 0.12 0.21
0.31 0.23 trace trace amount amount Li.sub.2O 0.75 0.60 0.50 0.50
-- -- 0.48 Fe.sub.2O.sub.3 0.46 0.45 0.45 0.44 trace trace 0.18
amount amount TiO.sub.2 0.34 0.62 0.52 0.48 trace trace 0.12 amount
amount SrO 0.55 -- 0.70 -- -- -- -- CeO.sub.2 -- -- 0.05 0.10 -- --
-- Ratio C1 0.357 0.317 0.309 0.318 0.385 0.385 0.260 C2 8.40 10.13
8.85 9.78 -- -- -- C3 0.268 0.248 0.245 0.260 0.154 0.100 0.130
Parameter Forming 1306 1321 1306 1303 1571 1430 1278 temperature/
.degree. C. Liquidus 1212 1216 1206 1205 1470 1350 1210
temperature/ .degree. C. .DELTA.T/.degree. C. 94 105 100 98 101 80
68 Elastic 96.3 95.6 95.2 95.8 90 89 88 modulus/ GPa Tensile 3560
3490 3460 3530 3460 2750 2500 strength/ MPa Crystallization 14 10 8
9 100 70 35 area ratio/% Amount of 8 11 7 8 40 30 25
bubbles/pcs
It can be seen from the values in the above tables that, compared
with the S glass, the composition for producing a glass fiber of
the present invention has the following advantages: (1) much higher
elastic modulus; (2) much lower liquidus temperature and much lower
crystallization area ratio, which indicate a low upper limit
temperature for crystallization as well as a low crystallization
rate and thus help to reduce the crystallization risk and increase
the fiber drawing efficiency; and (3) smaller amount of bubbles,
which indicates a better refining of molten glass.
In addition, compared with the traditional R glass and improved R
glass, the composition for producing a glass fiber of the present
invention has the following advantages: (1) much higher elastic
modulus and strength; (2) much lower crystallization area ratio,
which indicate a low crystallization rate and thus helps to reduce
the crystallization risk and increase the fiber drawing efficiency;
and (3) smaller amount of bubbles, which indicates a better
refining of molten glass.
Both S glass and traditional R glass cannot enable the achievement
of large-scale production with refractory-lined furnaces and, with
respect to improved R glass, part of the glass properties is
compromised to reduce the liquidus temperature and forming
temperature, so that the production difficulty is decreased and the
production with refractory-lined furnaces could be achieved. By
contrast, the composition for producing a glass fiber of the
present invention not only has a sufficiently low liquidus
temperature, forming temperature and crystallization rate which
enable the production with refractory-lined furnaces, but also
significantly increases the glass modulus and strength, thereby
resolving the technical bottleneck that the modulus and strength of
S glass fiber cannot be improved with the growth of production
scale.
Therefore, it can be seen from the above that, compared with the
current main-stream high-performance glasses, the composition for
producing a glass fiber of the present invention has made a
breakthrough in terms of elastic modulus, strength, crystallization
rate and refining performance of the glass, with significantly
improved modulus and strength, remarkably reduced crystallization
rate and relatively small amount of bubbles under the same
conditions. Thus, the overall technical solution of the present
invention enables an easy achievement of large-scale production
with refractory-lined furnaces.
The composition for producing a glass fiber according to the
present invention can be used for making glass fibers having the
aforementioned properties.
The composition for producing a glass fiber according to the
present invention in combination with one or more organic and/or
inorganic materials can be used for preparing composite materials
having improved characteristics, such as glass fiber reinforced
base materials.
The composition for producing a glass fiber of the present
invention not only results in glass fiber having a sufficiently low
liquidus temperature, forming temperature and crystallization rate
which enable the production with refractory-lined furnaces, but
also significantly increases the glass modulus and strength of the
glass fibers, thereby resolving the technical bottleneck that the
modulus and strength of S glass fiber cannot be improved with the
enhanced production scale. Compared with the current main-stream
high-performance glasses, the composition for producing a glass
fiber of the present invention has made a breakthrough in terms of
elastic modulus, strength, crystallization rate and refining
performance of the glass, with significantly improved modulus and
strength, remarkably reduced crystallization rate and relatively
small amount of bubbles under the same conditions. Thus, the
overall technical solution of the present invention enables an easy
achievement of large-scale production with refractory-lined
furnaces.
Unless otherwise indicated, the numerical ranges involved in the
invention include the end values. While particular embodiments of
the invention have been shown and described, it will be obvious to
those skilled in the art that changes and modifications may be made
without departing from the invention in its broader aspects, and
therefore, the aim in the appended claims is to cover all such
changes and modifications as fall within the true spirit and scope
of the invention.
* * * * *